CN113388209B - Low-temperature foamable self-adhesive expansion rubber block with high expansion rate and preparation method thereof - Google Patents

Low-temperature foamable self-adhesive expansion rubber block with high expansion rate and preparation method thereof Download PDF

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CN113388209B
CN113388209B CN202110687454.0A CN202110687454A CN113388209B CN 113388209 B CN113388209 B CN 113388209B CN 202110687454 A CN202110687454 A CN 202110687454A CN 113388209 B CN113388209 B CN 113388209B
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foaming
temperature
zinc
ethylene propylene
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CN113388209A (en
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谢宇
倪敏杰
何园明
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Haicheng New Materials Wuhu Co ltd
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Haicheng New Materials Wuhu Co ltd
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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    • C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
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Abstract

The invention discloses a self-adhesive expansion rubber block with high expansion rate, which can be foamed at low temperature, and comprises a rubber matrix, a vulcanization system, a foaming system and a tackifying system, wherein in order to achieve the matching of the vulcanization system and the foaming system, the vulcanization system adopts a mode of compounding sulfur and high-activity peroxide, the foaming system adopts a mode of compounding an AC foaming system and an OBSH foaming agent, and a foaming accelerator is matched to reduce the foaming temperature; according to the invention, the melt strength of the matrix is regulated by compounding the ethylene propylene diene monomer, the decomposition temperature of the foaming agent is reduced by compounding the accelerator with the AC foaming agent, and the vulcanization rate and the vulcanization temperature are regulated by compounding the high-activity peroxide with the sulfur system, so that the expansion rubber can reach high expansion multiplying power at a lower temperature, and the low-temperature self-adhesion performance of the expansion rubber block is improved by compounding a plurality of tackifying materials, so that the prepared expansion rubber block can simultaneously meet the requirements of the foaming rate and the adhesion.

Description

Low-temperature foamable self-adhesive expansion rubber block with high expansion rate and preparation method thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to a self-adhesive expansion rubber block with high expansion rate and capable of foaming at low temperature and a preparation method thereof.
Background
With the consumer upgrade of the automobile industry, higher requirements are put on the comfort of the automobile, and the NVH performance of the automobile is one of key performances for determining the comfort of the automobile, wherein a bypass sealing technology is an important component for improving the NVH performance of the automobile and mainly comprises a 3 Dbaffe injection molding piece and a 2D expansion rubber block, and compared with the 3D injection molding piece, the 2D expansion rubber block is more suitable for a cavity with a narrower irregularly-shaped space;
in the prior art, the inventor focuses on the foaming rate and the adhesiveness, but the foaming rate and the adhesiveness are difficult to meet at the same time, so that a double-layer design is mainly selected on the market at present, namely, the double-layer design consists of a foaming layer and an adhesive layer, but the foaming layer has no adhesiveness, so that the problem of poor sealing exists, meanwhile, the existence of the adhesive layer is not in line with the current trend of light weight of automobiles, the patent application with publication number of CN110372964A discloses a method for obtaining a self-adhesive expansion adhesive block through adding tackifying resin and halogenating modification of a matrix, the problems of the foaming rate and the self-adhesiveness are solved, a cavity with the same size is blocked, the required adhesive block has lighter weight, however, the inventor does not pay attention to the foaming temperature, and the used AC foaming agent does not support low-temperature foaming;
at present, energy conservation and cost reduction become important improvement directions of automobile enterprises, major automobile main engine factories have a plan for reducing furnace temperature, and the low-temperature foaming of a 2D expansion rubber block becomes important, but the low-temperature foaming of the existing self-adhesive expansion rubber block cannot be achieved, so that the invention provides the self-adhesive expansion rubber block with high expansion rate capable of being foamed at low temperature and a preparation method thereof to solve the problems in the prior art.
Disclosure of Invention
The invention aims to solve the problems and provide a self-adhesive expansion rubber block with high expansion rate capable of foaming at low temperature and a preparation method thereof.
In order to achieve the purpose of the invention, the invention is realized by the following technical scheme: the self-adhesive expansion rubber block with high expansion rate capable of foaming at low temperature comprises a rubber matrix, a vulcanization system, a foaming system and a tackifying system, wherein the vulcanization rate of the vulcanization system is matched with the foaming rate of the foaming system.
The further improvement is that: the rubber matrix is composed of more than two ethylene propylene diene monomer rubbers.
The further improvement is that: the rubber matrix is obtained by compounding POE elastomer with ethylene propylene diene monomer.
The further improvement is that: the vulcanizing system adopts a mode of compounding a sulfur system and high-activity peroxide, the mass ratio of the sulfur system to the high-activity peroxide is 10-5:1, the high-activity peroxide is selected from one of benzoyl peroxide, dicumyl peroxide, 1-di-3, 5-trimethylcyclohexane and diisopropylbenzene, the sulfur system adopts a mode of compounding sulfur and an accelerator, and the accelerator is selected from one or more of dithiocarbamates, thiurams, thiazoles, sulfenamides and guanidine.
The further improvement is that: the foaming system consists of an AC foaming system and an OBSH foaming agent, the mass ratio of the AC foaming system to the OBSH foaming agent is 1-10:1, and the foaming temperature is reduced by matching with a foaming accelerator, wherein the foaming accelerator is one or more selected from zinc oxide, zinc carbonate, zinc p-toluenesulfonate, sodium acetate, sodium stearate and modified urea, so that the AC foaming agent is rapidly decomposed in a temperature environment of 150 ℃.
The further improvement is that: the tackifying system comprises liquid rubber and tackifying resin, wherein the liquid rubber is selected from one or more of liquid polyisobutylene, liquid polybutadiene and modified products thereof, liquid polyisoprene, liquid ethylene propylene diene monomer and modified products thereof, and is matched with paraffin oil to adjust the viscosity to a specified viscosity, and the tackifying resin is selected from one or more of C5 tackifying resin, C9 tackifying resin and hydrogenated products thereof.
The preparation method of the self-adhesive expansion glue block with high expansion rate capable of foaming at low temperature comprises the following steps:
step one: preparation of masterbatch
Firstly, mixing a rubber matrix and a tackifying system by using a double-roll open mill, an internal mixer, an extruder and a dispersion blending device at the temperature of 140 ℃ to prepare master batch;
step two: product shaping
According to the first step, the master batch, the vulcanizing system and the foaming system are dispersed and mixed in a normal temperature environment by utilizing a double-roll open mill, an internal mixer, an extruder and a dispersion blending device to obtain a blend, and then the blend is extruded and molded to obtain the self-adhesive expansion rubber block product.
The beneficial effects of the invention are as follows: according to the invention, the melt strength of the matrix is regulated by compounding the ethylene propylene diene monomer, the decomposition temperature of the foaming agent is reduced by compounding the accelerator with the AC foaming agent, and the vulcanization rate and the vulcanization temperature are regulated by compounding the high-activity peroxide with the sulfur system, so that the expansion rubber can reach high expansion multiplying power at a lower temperature, and the low-temperature self-adhesion performance of the expansion rubber block is improved by compounding a plurality of tackifying materials, so that the prepared expansion rubber block can simultaneously meet the requirements of the foaming rate and the adhesion.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a flow chart of a preparation method of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that the directions or positional relationships indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," "third," "fourth," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
Example 1
The embodiment provides a self-adhesive expansion rubber block with high expansion rate, which can be foamed at low temperature and comprises the following raw materials: ethylene propylene diene monomer rubber Kalten 8550C:50 phr, ethylene propylene diene monomer rubber Kalten 2470C:50 phr, tackifying resin E-5400:30 phr, calcium carbonate: 110 phr, paraffin oil 500#:175 phr, polyisobutylene PB1300:60 phr, maleic anhydride modified polyisoprene MA-LNR:5 phr, AC blowing agent combination: 55 phr, oxo-bis-benzenesulfonic acid hydrazine OBSH foaming agent: 24 phr, sulfur S:4.5 phr, zinc oxide ZnO:14 phr, zinc di-n-butyldithiocarbamate BZ:5.6 phr, tetramethylthiuram disulfide TMTD:5.6 phr, 2' -dithiodibenzothiazyl DM:2.8phr, 1-bis (tert-butylperoxy) -3, 5-trimethylcyclohexane. TM.40B: 0.5 phr, stearic acid SA:2 phr, wherein the AC blowing agent is combined as follows: AC-T blowing agent: 100 phr, zinc carbonate: 10 phr, modified urea: 2 phr.
Referring to fig. 1, the preparation method thereof is as follows:
adding all ethylene propylene diene monomer rubber, tackifying resin E-5400 and calcium carbonate into an internal mixer at the temperature of 140 ℃, adding 100 phr paraffin oil and 60 phr polyisobutylene PB1300 in a batch mode, blending for 2 hours, discharging to obtain a master batch, adding the master batch, maleic anhydride modified polyisoprene, a foaming agent, sulfur S, zinc oxide ZnO, zinc di-n-butyl dithiocarbamate BZ, tetramethylthiuram disulfide TMTD, 2' -dithiodibenzothiazole DM, 1-di (tert-butylperoxy) -3, 5-trimethylcyclohexane TM40B, stearic acid and the rest paraffin oil into the internal mixer at the temperature of normal temperature, blending for 1 hour, and finally extruding the obtained blend on an extruder at the temperature of 80 ℃ to obtain the self-adhesive expansion rubber block.
The foaming rate of the self-adhesive expansion rubber block at 180 ℃ is as follows: 940%, the foaming rate in 150 ℃ temperature environment is: 950%.
Example two
The embodiment provides a self-adhesive expansion rubber block with high expansion rate, which can be foamed at low temperature and comprises the following raw materials: ethylene propylene diene monomer rubber Kalten 8550C:50 phr, ethylene propylene diene monomer rubber Kalten 2470C:40 phr, polyolefin elastomer POE:10 phr, tackifying resin E-5400:30 phr, calcium carbonate: 110 phr, paraffin oil 500#:175 phr, polyisobutylene PB1300:60 phr, maleic anhydride modified polyisoprene MA-LNR:5 phr, AC blowing agent combination: 55 phr, oxo-bis-benzenesulfonic acid hydrazine OBSH foaming agent: 24 phr, sulfur S:4.5 phr, zinc oxide ZnO:14 phr, zinc di-n-butyldithiocarbamate BZ:5.6 phr, tetramethylthiuram disulfide TMTD:5.6 phr, 2' -dithiodibenzothiazyl DM:2.8phr, 1-bis (tert-butylperoxy) -3, 5-trimethylcyclohexane. TM.40B: 0.5 phr, stearic acid SA:2 phr, wherein the AC blowing agent is combined as follows: AC-T blowing agent: 100 phr, zinc carbonate: 10 phr, modified urea: 2 phr.
Referring to fig. 1, the preparation method thereof is as follows:
all ethylene propylene diene monomer rubber, polyolefin elastomer POE, tackifying resin E-5400 and calcium carbonate are added into an internal mixer at 140 ℃, 100 phr paraffin oil and 60 phr polyisobutylene PB1300 are added in a batch mode, the mixture is blended for 2 hours, the discharged material is master batch, then the master batch, maleic anhydride modified polyisoprene, foaming agent, sulfur S, zinc oxide ZnO, zinc di-n-butyl dithiocarbamate BZ, tetramethylthiuram disulfide TMTD, 2' -dithiodibenzothiazole DM, 1-di (tert-butylperoxy) -3, 5-trimethylcyclohexane TM40B, stearic acid and the rest paraffin oil are added into the internal mixer at normal temperature, and finally the obtained blend is extruded and molded on an extruder at 80 ℃ to obtain self-adhesive expansion rubber blocks.
Example III
The embodiment provides a self-adhesive expansion rubber block with high expansion rate, which can be foamed at low temperature and comprises the following raw materials: ethylene propylene diene monomer rubber KEP 2480:50 phr, ethylene propylene diene monomer rubber Kalten 2470C:50 phr, tackifying resin E-5400:30 phr, calcium carbonate: 110 phr, paraffin oil 500#:175 phr, polyisobutylene PB1300:60 phr, maleic anhydride modified polyisoprene MA-LNR:5 phr, AC blowing agent combination: 55 phr, oxo-bis-benzenesulfonic acid hydrazine OBSH foaming agent: 24 phr, sulfur S:4.5 phr, zinc oxide ZnO:14 phr, zinc di-n-butyldithiocarbamate BZ:5.6 phr, tetramethylthiuram disulfide TMTD:5.6 phr, 2' -dithiodibenzothiazyl DM:2.8phr, 1-bis (tert-butylperoxy) -3, 5-trimethylcyclohexane. TM.40B: 0.5 phr, stearic acid SA:2 phr, wherein the AC blowing agent is combined as follows: AC-T blowing agent: 100 phr, zinc carbonate: 10 phr, modified urea: 2 phr.
Referring to fig. 1, the preparation method thereof is as follows:
adding all ethylene propylene diene monomer rubber, tackifying resin E-5400 and calcium carbonate into an internal mixer at the temperature of 140 ℃, adding 100 phr paraffin oil and 60 phr polyisobutylene PB1300 in a batch mode, blending for 2 hours, discharging to obtain a master batch, adding the master batch, maleic anhydride modified polyisoprene, a foaming agent, sulfur S, zinc oxide ZnO, zinc di-n-butyl dithiocarbamate BZ, tetramethylthiuram disulfide TMTD, 2' -dithiodibenzothiazole DM, 1-di (tert-butylperoxy) -3, 5-trimethylcyclohexane TM40B, stearic acid and the rest paraffin oil into the internal mixer at the temperature of normal temperature, blending for 1 hour, and finally extruding the obtained blend on an extruder at the temperature of 80 ℃ to obtain the self-adhesive expansion rubber block.
Comparative example one
The embodiment provides a self-adhesive expansion rubber block with high expansion rate, which can be foamed at low temperature and comprises the following raw materials: ethylene propylene diene monomer rubber Kalten 8550C:100 phr, tackifying resin E-5400:30 phr, calcium carbonate: 110 phr, paraffin oil 500#:175 phr, polyisobutylene PB1300:60 phr, maleic anhydride modified polyisoprene MA-LNR:5 phr, AC blowing agent combination: 55 phr, oxo-bis-benzenesulfonic acid hydrazine OBSH foaming agent: 24 phr, sulfur S:4.5 phr, zinc oxide ZnO:14 phr, zinc di-n-butyldithiocarbamate BZ:5.6 phr, tetramethylthiuram disulfide TMTD:5.6 phr, 2' -dithiodibenzothiazyl DM:2.8phr, 1-bis (tert-butylperoxy) -3, 5-trimethylcyclohexane. TM.40B: 0.5 phr, stearic acid SA:2 phr, wherein the AC blowing agent is combined as follows: AC-T blowing agent: 100 phr, zinc carbonate: 10 phr, modified urea: 2 phr.
Referring to fig. 1, the preparation method thereof is as follows:
adding all ethylene propylene diene monomer rubber, tackifying resin E-5400 and calcium carbonate into an internal mixer at the temperature of 140 ℃, adding 100 phr paraffin oil and 60 phr polyisobutylene PB1300 in a batch mode, blending for 2 hours, discharging to obtain a master batch, adding the master batch, maleic anhydride modified polyisoprene, a foaming agent, sulfur S, zinc oxide ZnO, zinc di-n-butyl dithiocarbamate BZ, tetramethylthiuram disulfide TMTD, 2' -dithiodibenzothiazole DM, 1-di (tert-butylperoxy) -3, 5-trimethylcyclohexane TM40B, stearic acid and the rest paraffin oil into the internal mixer at the temperature of normal temperature, blending for 1 hour, and finally extruding the obtained blend on an extruder at the temperature of 80 ℃ to obtain the self-adhesive expansion rubber block.
Comparative example two
The embodiment provides a self-adhesive expansion rubber block with high expansion rate, which can be foamed at low temperature and comprises the following raw materials: ethylene propylene diene monomer rubber Kalten 8550C:90 phr (phr); polyolefin elastomer POE:10 phr, tackifying resin E-5400:30 phr, calcium carbonate: 110 phr, paraffin oil 500#:175 phr, polyisobutylene PB1300:60 phr, maleic anhydride modified polyisoprene MA-LNR:5 phr, AC blowing agent combination: 55 phr, oxo-bis-benzenesulfonic acid hydrazine OBSH foaming agent: 24 phr, sulfur S:4.5 phr, zinc oxide ZnO:14 phr, zinc di-n-butyldithiocarbamate BZ:5.6 phr, tetramethylthiuram disulfide TMTD:5.6 phr, 2' -dithiodibenzothiazyl DM:2.8phr, 1-bis (tert-butylperoxy) -3, 5-trimethylcyclohexane. TM.40B: 0.5 phr, stearic acid SA:2 phr, wherein the AC blowing agent is combined as follows: AC-T blowing agent: 100 phr, zinc carbonate: 10 phr, modified urea: 2 phr.
Referring to fig. 1, the preparation method thereof is as follows:
all ethylene propylene diene monomer rubber, polyolefin elastomer POE, tackifying resin E-5400 and calcium carbonate are added into an internal mixer at 140 ℃, 100 phr paraffin oil and 60 phr polyisobutylene PB1300 are added in a batch mode, the mixture is blended for 2 hours, the discharged material is master batch, then the master batch, maleic anhydride modified polyisoprene, foaming agent, sulfur S, zinc oxide ZnO, zinc di-n-butyl dithiocarbamate BZ, tetramethylthiuram disulfide TMTD, 2' -dithiodibenzothiazole DM, 1-di (tert-butylperoxy) -3, 5-trimethylcyclohexane TM40B, stearic acid and the rest paraffin oil are added into the internal mixer at normal temperature, and finally the obtained blend is extruded and molded on an extruder at 80 ℃ to obtain self-adhesive expansion rubber blocks.
Comparative example III
The embodiment provides a self-adhesive expansion rubber block with high expansion rate, which can be foamed at low temperature and comprises the following raw materials: ethylene propylene diene monomer rubber Kalten 8550C:50 phr, ethylene propylene diene monomer rubber Kalten 2470C:50 phr, tackifying resin E-5400:30 phr, calcium carbonate: 110 phr, paraffin oil 500#:175 phr, polyisobutylene PB1300:60 phr, maleic anhydride modified polyisoprene MA-LNR:5 phr, AC-T blowing agent: 55 phr, oxo-bis-benzenesulfonic acid hydrazine OBSH foaming agent: 24 phr, sulfur S:4.5 phr, zinc oxide ZnO:14 phr, zinc di-n-butyldithiocarbamate BZ:5.6 phr, tetramethylthiuram disulfide TMTD:5.6 phr, 2' -dithiodibenzothiazyl DM:2.8phr, 1-bis (tert-butylperoxy) -3, 5-trimethylcyclohexane. TM.40B: 0.5 phr, stearic acid SA:2 phr.
Referring to fig. 1, the preparation method thereof is as follows:
adding all ethylene propylene diene monomer rubber, tackifying resin E-5400 and calcium carbonate into an internal mixer at the temperature of 140 ℃, adding 100 phr paraffin oil and 60 phr polyisobutylene PB1300 in a batch mode, blending for 2 hours, discharging to obtain a master batch, adding the master batch, maleic anhydride modified polyisoprene, a foaming agent, sulfur S, zinc oxide ZnO, zinc di-n-butyl dithiocarbamate BZ, tetramethylthiuram disulfide TMTD, 2' -dithiodibenzothiazole DM, 1-di (tert-butylperoxy) -3, 5-trimethylcyclohexane TM40B, stearic acid and the rest paraffin oil into the internal mixer at the temperature of normal temperature, blending for 1 hour, and finally extruding the obtained blend on an extruder at the temperature of 80 ℃ to obtain the self-adhesive expansion rubber block.
Comparative example four
The embodiment provides a self-adhesive expansion rubber block with high expansion rate, which can be foamed at low temperature and comprises the following raw materials: ethylene propylene diene monomer rubber Kalten 8550C:50 phr, ethylene propylene diene monomer rubber Kalten 2470C:50 phr, tackifying resin E-5400:30 phr, calcium carbonate: 110 phr, paraffin oil 500#:175 phr, polyisobutylene PB1300:60 phr, maleic anhydride modified polyisoprene MA-LNR:5 phr, AC blowing agent combination: 55 phr, oxo-bis-benzenesulfonic acid hydrazine OBSH foaming agent: 24 phr, sulfur S:4.5 phr, zinc oxide ZnO:14 phr, zinc di-n-butyldithiocarbamate BZ:5.6 phr, tetramethylthiuram disulfide TMTD:5.6 phr, 2' -dithiodibenzothiazyl DM:2.8phr, stearic acid SA:2 phr, wherein the AC blowing agent is combined as follows: AC-T blowing agent: 100 phr, zinc carbonate: 10 phr, modified urea: 2 phr.
Referring to fig. 1, the preparation method thereof is as follows:
adding all ethylene propylene diene monomer rubber, tackifying resin E-5400 and calcium carbonate into an internal mixer at 140 ℃, adding 100 phr paraffin oil and 60 phr polyisobutylene PB1300 in a batch mode, blending for 2 hours, discharging to obtain a master batch, adding the master batch, maleic anhydride modified polyisoprene, a foaming agent, sulfur S, zinc oxide ZnO, zinc di-n-butyl dithiocarbamate BZ, tetramethylthiuram disulfide TMTD, 2' -dithiodibenzothiazole DM, stearic acid and the rest paraffin oil into the internal mixer at normal temperature, blending for 1 hour, and finally extruding the obtained blend on an extruder at 80 ℃ to obtain the self-adhesive expansion rubber block.
Comparative example five
The embodiment provides a self-adhesive expansion rubber block with high expansion rate, which can be foamed at low temperature and comprises the following raw materials: ethylene propylene diene monomer rubber Kalten 8550C:50 phr, ethylene propylene diene monomer rubber Kalten 2470C:50 phr, tackifying resin E-5400:30 phr, calcium carbonate: 110 phr, paraffin oil 500#:235 phr, maleic anhydride modified polyisoprene MA-LNR:5 phr, AC blowing agent combination: 55 phr, oxo-bis-benzenesulfonic acid hydrazine OBSH foaming agent: 24 phr, sulfur S:4.5 phr, zinc oxide ZnO:14 phr, zinc di-n-butyldithiocarbamate BZ:5.6 phr, tetramethylthiuram disulfide TMTD:5.6 phr, 2' -dithiodibenzothiazyl DM:2.8phr, 1-bis (tert-butylperoxy) -3, 5-trimethylcyclohexane. TM.40B: 0.5 phr, stearic acid SA:2 phr, wherein the AC blowing agent is combined as follows: AC-T blowing agent: 100 phr, zinc carbonate: 10 phr, modified urea: 2 phr.
Referring to fig. 1, the preparation method thereof is as follows:
adding all ethylene propylene diene monomer rubber, tackifying resin E-5400 and calcium carbonate into an internal mixer at 140 ℃, adding 100 phr paraffin oil 0, blending for 2 hours, discharging to obtain master batch, then adding the master batch, maleic anhydride modified polyisoprene, foaming agent, sulfur S, zinc oxide ZnO, zinc di-n-butyl dithio carbamate BZ, tetramethylthiuram disulfide TMTD, 2' -dithio dibenzothiazyl DM, 1-di (tert-butyl peroxy) -3, 5-trimethylcyclohexane TM40B, stearic acid and the rest paraffin oil into the internal mixer at normal temperature, blending for 1 hour, and finally extruding the obtained blend on an extruder at 80 ℃ to obtain the self-adhesive expansion rubber block.
The specific compositions of the respective raw materials in the above examples and comparative examples are shown in Table 1:
TABLE 1
Material Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
EPDM Kalten 8550C 50 50 100 90 50 50 50
EPDM Kalten 2470C 50 40 50 50 50 50
EPDM KEP 2480 50
POE 10 10
E-5400 30 30 30 30 30 30 30 30
Calcium carbonate 110 110 110 110 110 110 110 110
Paraffin oil 500# 175 175 175 175 175 175 175 235
PB1300 60 60 60 60 60 60 60 0
MA-LNR 5 5 5 5 5 5 5 5
AC blowing agent combinations 55 55 55 55 55 55 55
AC-T foaming agent 55
OBSH 24 24 24 24 24 24 24 24
S 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5
BZ 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6
TMTD 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6
DM 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8
Zinc oxide 14 14 14 14 14 14 14 14
Stearic acid 2 2 2 2 2 2 2 2
TM40B 0.5 0.5 0.5 0.5 0.5 0.5 0.5
The properties of the expansion joint strips corresponding to the components of examples 1-3 and comparative examples 1-5 are shown in Table 2:
TABLE 2
Performance of Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
Foaming ratio at 150 DEG C 1010% 1120% 1008% 550% 610% 540% 420% 908%
Foaming rate at 180 DEG C 998% 1030% 965% 889% 987% 998% 670% 984%
Initial tackiness at-5 DEG C Good (good) Good (good) Good (good) Good (good) Good (good) Good (good) Good (good) Difference of difference
Water absorption rate 2.5% 2.8% 3.0% 2.6% 2.9% 3.0% 49% 5.8%
The results in tables 1 and 2 show that the low-temperature foaming effect can be well achieved by compounding the ethylene propylene diene monomer, the AC foaming agent combination and the vulcanization system, and the foaming ratio is higher than 900%. For example, the compounded ethylene propylene diene monomer matrix of example 1 can achieve a higher low temperature foaming rate than comparative example 1 due to the appropriate melt strength. In addition, comparative examples 1 and 3, it can be seen that the foaming temperature of the AC blowing agent composition to which the foaming activator was added was lower than that of the AC-T blowing agent; finally, comparative examples 1 and 5 have found that excellent-5℃initial tackiness can be achieved by adding a liquid rubber as a tackifier.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (3)

1. The self-adhesive expansion rubber block capable of foaming at low temperature and high in expansion rate is characterized by comprising the following raw materials in parts by weight: ethylene propylene diene monomer rubber Kalten 8550C:50 phr, ethylene propylene diene monomer rubber Kalten 2470C:50 phr, tackifying resin E-5400:30 phr, calcium carbonate: 110 phr, paraffin oil 500#:175 phr, polyisobutylene PB1300:60 phr, maleic anhydride modified polyisoprene MA-LNR:5 phr, AC blowing agent combination: 55 phr, oxo-bis-benzenesulfonic acid hydrazine OBSH foaming agent: 24 phr, sulfur S:4.5 phr, zinc oxide ZnO:14 phr, zinc di-n-butyldithiocarbamate BZ:5.6 phr, tetramethylthiuram disulfide TMTD:5.6 phr, 2' -dithiodibenzothiazyl DM:2.8phr, 1-bis (tert-butylperoxy) -3, 5-trimethylcyclohexane. TM.40B: 0.5 phr, stearic acid SA:2 phr, wherein the AC blowing agent is combined as follows: AC-T blowing agent: 100 phr, zinc carbonate: 10 phr, modified urea: 2 phr;
the preparation method comprises the following steps:
adding all ethylene propylene diene monomer rubber, tackifying resin E-5400 and calcium carbonate into an internal mixer at the temperature of 140 ℃, adding 100 phr paraffin oil and 60 phr polyisobutylene PB1300 in a batch mode, blending for 2 hours, discharging to obtain a master batch, adding the master batch, maleic anhydride modified polyisoprene, a foaming agent, sulfur S, zinc oxide ZnO, zinc di-n-butyl dithiocarbamate BZ, tetramethylthiuram disulfide TMTD, 2' -dithiodibenzothiazole DM, 1-di (tert-butylperoxy) -3, 5-trimethylcyclohexane TM40B, stearic acid and the rest paraffin oil into the internal mixer at the temperature of normal temperature, blending for 1 hour, and finally extruding the obtained blend on an extruder at the temperature of 80 ℃ to obtain the self-adhesive expansion rubber block.
2. The self-adhesive expansion rubber block capable of foaming at low temperature and high in expansion rate is characterized by comprising the following raw materials in parts by weight: ethylene propylene diene monomer rubber Kalten 8550C:50 phr, ethylene propylene diene monomer rubber Kalten 2470C:40 phr, polyolefin elastomer POE:10 phr, tackifying resin E-5400:30 phr, calcium carbonate: 110 phr, paraffin oil 500#:175 phr, polyisobutylene PB1300:60 phr, maleic anhydride modified polyisoprene MA-LNR:5 phr, AC blowing agent combination: 55 phr, oxo-bis-benzenesulfonic acid hydrazine OBSH foaming agent: 24 phr, sulfur S:4.5 phr, zinc oxide ZnO:14 phr, zinc di-n-butyldithiocarbamate BZ:5.6 phr, tetramethylthiuram disulfide TMTD:5.6 phr, 2' -dithiodibenzothiazyl DM:2.8phr of 1, 1-bis (tert-butylperoxy) -3, 5-trimethylcyclohexane TM40B:0.5 phr, stearic acid SA:2 phr, wherein the AC blowing agent is combined as follows: AC-T blowing agent: 100 phr, zinc carbonate: 10 phr, modified urea: 2 phr;
the preparation method comprises the following steps:
all ethylene propylene diene monomer rubber, polyolefin elastomer POE, tackifying resin E-5400 and calcium carbonate are added into an internal mixer at 140 ℃, 100 phr paraffin oil and 60 phr polyisobutylene PB1300 are added in a batch mode, the mixture is blended for 2 hours, the discharged material is master batch, then the master batch, maleic anhydride modified polyisoprene, foaming agent, sulfur S, zinc oxide ZnO, zinc di-n-butyl dithiocarbamate BZ, tetramethylthiuram disulfide TMTD, 2' -dithiodibenzothiazole DM, 1-di (tert-butylperoxy) -3, 5-trimethylcyclohexane TM40B, stearic acid and the rest paraffin oil are added into the internal mixer at normal temperature, and finally the obtained blend is extruded and molded on an extruder at 80 ℃ to obtain self-adhesive expansion rubber blocks.
3. The self-adhesive expansion rubber block capable of foaming at low temperature and high in expansion rate is characterized by comprising the following raw materials in parts by weight: ethylene propylene diene monomer rubber KEP 2480:50 phr, ethylene propylene diene monomer rubber Kalten 2470C:50 phr, tackifying resin E-5400:30 phr, calcium carbonate: 110 phr, paraffin oil 500#:175 phr, polyisobutylene PB1300:60 phr, maleic anhydride modified polyisoprene MA-LNR:5 phr, AC blowing agent combination: 55 phr, oxo-bis-benzenesulfonic acid hydrazine OBSH foaming agent: 24 phr, sulfur S:4.5 phr, zinc oxide ZnO:14 phr, zinc di-n-butyldithiocarbamate BZ:5.6 phr, tetramethylthiuram disulfide TMTD:5.6 phr, 2' -dithiodibenzothiazyl DM:2.8phr, 1-bis (tert-butylperoxy) -3, 5-trimethylcyclohexane. TM.40B: 0.5 phr, stearic acid SA:2 phr, wherein the AC blowing agent is combined as follows: AC-T blowing agent: 100 phr, zinc carbonate: 10 phr, modified urea: 2 phr;
the preparation method comprises the following steps:
adding all ethylene propylene diene monomer rubber, tackifying resin E-5400 and calcium carbonate into an internal mixer at the temperature of 140 ℃, adding 100 phr paraffin oil and 60 phr polyisobutylene PB1300 in a batch mode, blending for 2 hours, discharging to obtain a master batch, adding the master batch, maleic anhydride modified polyisoprene, a foaming agent, sulfur S, zinc oxide ZnO, zinc di-n-butyl dithiocarbamate BZ, tetramethylthiuram disulfide TMTD, 2' -dithiodibenzothiazole DM, 1-di (tert-butylperoxy) -3, 5-trimethylcyclohexane TM40B, stearic acid and the rest paraffin oil into the internal mixer at the temperature of normal temperature, blending for 1 hour, and finally extruding the obtained blend on an extruder at the temperature of 80 ℃ to obtain the self-adhesive expansion rubber block.
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